Minerals Engineering 5051 (2013) 140142

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Technical Note

Simultaneous sulde oxidation and gold leaching of a refractory gold

concentrate by chloridehypochlorite solution
Mehdi Ghobeiti Hasab, Fereshteh Rashchi , Shahram Raygan
School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In this research, oxidation of sulde and leaching of gold from a goldbearing sulde concentrate using
Received 17 June 2012 chloridehypochlorite solution has been investigated. Effects of calcium hypochlorite concentration, ini-
Accepted 28 August 2012 tial pH and sodium chloride concentration on the recovery of gold were examined. Two conditions were
Available online 11 October 2012
considered; the stability range of the gold complex (Eh > 900 mV) and formation of chlorine gas
(pH < 3.5). During leaching, due to oxidation of sulde and generation of acid, pH dropped. About 82%
Keywords: of gold was extracted from 200 g/L concentrate after 2 h using 200 g/L Ca(OCl)2, 200 g/L NaCl at initial
Refractory gold orel
pH of 11, stirring speed of 600 rpm and temperature of 25 C.
Oxidative pre-treatment
Non-cyanide leaching
2012 Elsevier Ltd. All rights reserved.

1. Introduction
Although cyanide is used commercially for the extraction of
gold, investigations have been done on alternative non-toxic
leachants such as chloride/hypochlorite (Puvvada and Murthy,
2000; Baghalha, 2007; Soo Nam et al., 2008).
Hypochlorite salt is ionized in water and at pH < 7.5, the hypo-
chlorite ion (OCl) is converted to hypochlorous acid (HOCl). At
high acidic conditions (pH < 3.5) aqueous chlorine (Cl2(aq)) is
formed and toxic chlorine gas is evolved from the solution. Among
these species, hypochlorous acid is the most effective oxidant (Jef-
frey et al., 2001). Oxidation of suldes by hypochlorous acid has
the advantage of sulfate formation instead of elemental sulfur
(reaction (1)) (Ikiz et al., 2006). In hypochlorous acid solution, gold
is dissolved and [AuCl4] complex forms according to reaction (2).
The [AuCl4] is stable at pH range of 08 and potentials greater
than 0.9 V (Nesbitt et al., 1990).
2FeS2 15HOCl 7H2 O ! 2FeOH3 4H2 SO4 15HCl
 
2Au 3HOCl 3H 5Cl ! 2AuCl4  3H2 O
In the present paper, simultaneous oxidative pretreatment and
gold leaching of a sulde concentrate using the chloride/hypochlo-
rite solution has been studied.
2. Experimental
The concentrate used in this study was obtained by otation of
a sample of an ore located in north-western of Iran (Barika Mine in
Corresponding author. Tel.: +98 21 88012999; fax: +98 21 88006076.
E-mail address: rashchi@ut.ac.ir (F. Rashchi).
Sardasht). The ore was ground to 90% ner than 37.4 lm (ca. 400
mesh). All the reagents used for leaching including NaCl, Ca(OCl)2
and H2SO4 were analytical grade from Merck. For leaching experi-
ments, the required reagents were added to a beaker containing
deionized water. Then, the concentrate was added into the lea-
chant solution in the beaker with solidliquid ratio of 1:5 and stir-
red on a magnetic stirrer at 600 rpm and at 25 C. During the
leaching, the slurry pH and ORP (vs. SHE, platinum electrode, mod-
el: SENTEK) were controlled. Slurry samples were taken at differ-
ent intervals by a syringe and ltered. The solutions were
analyzed for gold by ICP (model: VISTA-PRO). The solid residues
were washed, then dried and analyzed by XRD (model: Philips
Xpert with Cu Ka radiation).
3. Results and discussion
Fig. 1a shows that the concentrate is composed of major phases
1 of quartz (SiO2) and pyrite (FeS2) along with minor phases of
muscovite (H2KAl3(SiO4)3) and barite (BaSO4). The concentrate in-
cludes 17.76% Si, 13.68% S, 12.79% Fe, 5.93% Al, 2.26% K, 1.84% Ba
2
(analyzed by XRF, model: Philips PW1480), 20.45 ppm Au and
1650 ppm Ag (analyzed by re assay). Saba et al. (2011) worked
on the ore sample and showed that direct cyanide leaching after
24 h yielded ca. 54.8% gold recovery, while by diagnostic leaching
(cyanidation after dissolution of the sulde minerals using HCl,
H2SO4, FeCl3 and HNO3, respectively), the gold recovery increased
to 98.1%. This represents ultimate possible recovery of gold from
fully oxidized concentrate.
Fig. 2a and b shows the slurry pH and ORP as a function of time
at different concentrations of calcium hypochlorite with 100 g/L
NaCl. As shown, pH dropped as the concentrate was added to the
leach solution. This was attributed to the oxidation of sulde and

0892-6875/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
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 M.G. Hasab et al. / Minerals Engineering 5051 (2013) 140142 141

generation of acid. Decreasing pH to below 7.5, hypochlorous acid highest value. According to Fig. 2b it seems that 200 g/L calcium
becomes the dominant oxidant species and ORP reaches to its hypochlorite is adequate to obtain an oxidizing condition to stabi-
lize the gold complex. At higher concentrations of calcium hypo-
chlorite (e.g., 250 g/L) no signicant effect on pH and ORP occurs.

Fig. 1. XRD pattern of (a) the concentrate (b) solid residue after 2 h leaching (200 g/ Fig. 3. The percentage of leached gold as a function of leaching time at different
L Ca(OCl)2, initial pH = 11, 200 g/L NaCl). concentrations of Ca(OCl)2 and NaCl (initial pH = 11).

Fig. 2. The slurry pH and ORP as a function of leaching time at various conditions of (a, b) Ca(OCl)2 concentration, (c, d) initial pH and (e, f) NaCl concentration.
142 M.G. Hasab et al. / Minerals Engineering 5051 (2013) 140142
Fig. 4. SEM images of a FeS2 particle (a) before leaching, (b) after 30 min leaching and (c) after 120 min leaching (200 g/L Ca(OCl)2, initial pH = 11, 200 g/L NaCl).
Fig. 2c and d shows the pH and ORP changes of the slurry in the
presence of 100 g/L NaCl and 200 g/L Ca(OCl)2. Initial pHs were de-
creased by adding sulfuric acid. Decreasing the initial pH was not
useful, neither for the desired reaction nor for the safety issues
associated with the release of chlorine gas.
Fig. 2e and f shows effect of different chloride concentrations
(as NaCl) on the pH and ORP changes of the slurry. As shown, high-
er levels of NaCl signicantly enhanced the rate of pH drop, i.e., the
rate of sulde oxidation reaction. As the NaCl concentration in-
creased (e.g., 250 or 300 g/L), at higher pHs the conversion reaction
of hypochlorous acid species to chlorine species occurs; thus, chlo-
rine gas could be formed easier and due to escaping of the chlorine
oxidant from the solution, ORP drops rapidly. Therefore, 200 g/L
NaCl is the optimum amount required.
Fig. 3 shows the percentage of leached gold as a function of
leaching time at Ca(OCl)2NaCl concentrations of 200100, 250
100 and 200200 g/L. It is evident that increasing the concentra-
tion of NaCl unlike Ca(OCl)2 has signicant effect on the leaching
of gold. Approximately, 82% of gold was leached during 120 min
at experimental conditions of 200 g/L Ca(OCl)2, 200 g/L NaCl,
200 g/L concentrate, initial pH of 11, stirring speed of 600 rpm
and temperature of 25 C and after 120 min a plateau can be seen.
XRD pattern of washed solid residue after 120 min leaching
(Fig. 1b) shows that the phases of quartz, barite and muscovite
were not dissolved; however, most of the pyrite was oxidized. Oxi-
dation product of pyrite is amorphous Fe(OH)3 which was not de-
tected by XRD. Calcium sulfate as minor phase of CaSO40.5H2O
was also observed. This phase is formed due to the reaction be-
tween the sulphate species present in the system with Ca(II) ion re-
sulted from ionization of calcium hypochlorite.
In Fig. 4, high magnication images of a pyrite particle by SEM
(model: TESCAN) equipped with EDX (model: SAMx) have been
illustrated. Fig. 4a shows the concentrate before leaching. It is clear
that gold occurs as electrum (gold alloyed with silver) in associa-
tion with pyrite. Fig. 4b and c shows the residue after 30 and
120 min leaching, respectively. As it is shown the product of pyrite
oxidation, Fe(OH)3, covers the pyrite surface. Coating of this prod-
uct on the unreacted sulde surfaces probably decreases the recov-
ery of gold.
4. Conclusions
Combining sulde oxidation and gold leaching using chloride/
hypochlorite solution was used for a refractory sulde concentrate
containing 20.45 g/t gold. Leaching tests at different concentra-
tions of Ca(OCl)2 and NaCl, and also various initial pHs were per-
formed. Under optimum conditions (200 g/L Ca(OCl)2, initial
pH = 11 and 200 g/L NaCl), the recovery of gold after only 2 h
was about 82%.
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